Organic Chemistry

Organic Chemistry

At the end of this lecture, students

should be able to:

Specify types of reactions for alkyl

halides

Able to identify the mechanism involved
for a given reaction (unimolecular or
bimolecular)

Draw/write the reaction mechanism

Draw the energy diagram

General Features of Elimination

Elimination reactions involve the loss of elements
from the starting material to form a new bond in
the product.

General Features of Elimination

Equations [1] and [2] illustrate examples of
elimination reactions. In both reactions a base
removes the elements of an acid, HX, from the
organic starting material.

General Features of Elimination

Removal of the elements HX is called
dehydrohalogenation.
Dehydrohalogenation is an example of elimination.
The curved arrow formalism shown below illustrates
how four bonds are broken or formed in the process.

General Features of Elimination

The most common bases used in elimination
reactions are negatively charged oxygen
compounds, such as HO and its alkyl derivatives,
RO, called alkoxides.

General Features of Elimination

To draw any product of dehydrohalogenation
Find the carbon. Identify ALL carbons with H
atoms. Remove the elements of H and X form the
and carbons and form a bond.

Alkene: The Products of Elimination

Recall that the double bond of an alkene
consists of a bond and a bond.

Alkene: The Products of Elimination

Classification of Alkenes
Alkenes are classified according to the number
of carbon atoms bonded to the carbons of the
double bond.

Fig. Classifying alkenes by the number

of R groups bonded to the double bond

Alkene: The Products of Elimination

Recall that rotation about double bonds is
restricted.

Figure 8.2 Rotation around C-C and C=C compared

Alkene: The Products of Elimination

Because of restricted rotation, two stereoisomers
of 2-butene are possible. cis-2-Butene and trans2-butene are diastereomers, because they are
stereoisomers that are not mirror images of each
other.

Alkene: The Products of Elimination

Whenever the two groups on each end of a
carbon-carbon double bond are different from
each other, two diastereomers are possible.

Alkene: The Products of Elimination

In general, trans alkenes are more stable than cis
alkenes because the groups bonded to the
double bond carbons are further apart,
reducing steric interactions.

Alkene: The Products of Elimination

The stability of an alkene increases as the
number of R groups bonded to the double bond
carbons increases.

The higher the percent s-character, the more readily

an atom accepts electron density. Thus, sp2 carbons
are more able to accept electron density and sp3
carbons are more able to donate electron density.
Consequently, increasing the number of electron
donating groups on a carbon atom able to accept
electron density makes the alkene more stable.

Alkene: The Products of Elimination

trans-2-Butene (a disubstituted alkene) is more
stable than cis-2-butene (another disubstituted
alkene), but both are more stable than 1-butene
(a monosubstituted alkene).

An elimination involves the

loss of two atoms or groups
from the substrate, usually
with formation of a bond.
Depending on the reagents and conditions
involved, an elimination might be a first order
(E1) or second-order (E2) process.

Mechanisms of Elimination

There are TWO mechanisms of

eliminationE2 and E1, just as there are two
mechanisms of substitution, SN2 and SN1.
E2 mechanismbimolecular elimination
E1 mechanismunimolecular elimination

The E2 and E1 mechanisms differ in the

timing of bond cleavage and bond
formation, analogous to the SN2 and SN1
mechanisms.
E2 and SN2 reactions have some features
in common, as do E1 and SN1 reactions.

Mechanisms of EliminationE2
The most common mechanism for
dehydrohalogenation is the E2 mechanism.
It exhibits second-order kinetics, and both the
alkyl halide and the base appear in the rate
equation i.e.

rate = k[(CH3)3CBr][OH]
The reaction is concertedall bonds are broken
and formed in a single step.

Mechanisms of EliminationE2

Mechanisms of EliminationE2
An energy diagram for the E2 reaction

(CH3)3CBr + OH (CH3)2C=CH2 + H2O + Br

In the transition state, the CH and CBr bonds are partially broken, The
OH and bonds are partially formed, and both the base and the
departing leaving group bear a partial negative charge.

Mechanisms of EliminationE2
There are close parallels between E2 and SN2
mechanisms in how the identity of the base, the
leaving group and the solvent affect the rate.
The base appears in the rate equation, so the
rate of the E2 reaction increases as the strength
of the base increases.
E2 reactions are generally run with strong,
negatively charged bases like OH and OR.

Mechanisms of EliminationE2

Mechanisms of EliminationE2
The SN2 and E2 mechanisms differ in how the R
group affects the reaction rate.

Mechanisms of EliminationE2
Increasing the number of R groups on the carbon
with the leaving group forms more highly
substituted, more stable alkenes in E2 reactions.
In the reactions below, since the disubstituted
alkene is more stable, the 3 alkyl halide reacts
faster than the 1 alkyl halide.

 Recall that when alkyl halides have two or more

different carbons, more than one alkene
product is formed.
When this happens, one of the products usually
predominates.
The major product is the more stable product
the one with the more substituted double bond.
This phenomenon is called the Zaitsev rule.

The Zaitsev rule: the major product in elimination has

the more substituted double bond.
A reaction is regioselective when it yields predominantly or
exclusively one constitutional isomer when more than one
is possible. Thus, the E2 reaction is regioselective.

 When a mixture of stereoisomers is possible from

a dehydrohalogenation, the major product is the
more stable stereoisomer.
A reaction is stereoselective when it forms
predominantly or exclusively one stereoisomer
when two or more are possible.
The E2 reaction is stereoselective because one
stereoisomer is formed preferentially.

Mechanisms of EliminationE1
The dehydrohalogenation of (CH3)3CI with H2O
to form (CH3)2C=CH2 can be used to illustrate
the second general mechanism of elimination,
the E1 mechanism.
An E1 reaction exhibits first-order kinetics:

rate = k[(CH3)3CI]
The E1 reaction proceed via a two-step
mechanism:
the bond to the leaving group breaks first
before the bond is formed.
The slow step is unimolecular, involving only
the alkyl halide.

Mechanisms of EliminationE1

The E1 and E2 mechanisms both involve

the same number of bonds broken and
formed.
The only difference is TIMING.

In an E1, the leaving group comes off before

the proton is removed, and the reaction
occurs in TWO steps.
In an E2 reaction, the leaving group comes
off as the proton is removed, and the
reaction occurs in ONE step.

Mechanisms of EliminationE1

Mechanisms of EliminationE1
An energy diagram for the E1 reaction

(CH3)3CI + OH (CH3)2C=CH2 + H2O + I

Since the E1 mechanism has two steps, there are two energy barriers.
Step (1) is rate-determining; Ea[1]>Ea[2]

Mechanisms of EliminationE1
The rate of an E1 reaction increases as the number of R
groups on the carbon with the leaving group increases.

The strength of the base usually determines whether a

reaction follows the E1 or E2 mechanism. Strong bases
like OH and OR favor E2 reactions, whereas weaker
bases like H2O and ROH favor E1 reactions.

Mechanisms of EliminationE1
E1 reactions are regioselective, favoring
formation of the more substituted, more stable
alkene.
Zaitsevs rule applies to E1 reactions also.

SN1 and E1 Reactions

SN1 and E1 reactions have exactly the same first
stepformation of a carbocation. They differ in
what happens to the carbocation.

Because E1 reactions often occur with a

competing SN1 reaction, E1 reactions of alkyl
halides are much less useful than E2 reactions.

When is the Mechanism E1 or E2?

The strength of the base is the most important factor in

determining the mechanism for elimination.
Strong bases favor the E2 mechanism. Weak bases favor
the E1 mechanism.

Summary

E2 Reactions and Alkyne Synthesis

A single elimination reaction produces a bond
of an alkene.
Two consecutive elimination reactions produce
two bonds of an alkyne.

E2 Reactions and Alkyne Synthesis

Two elimination reactions are needed to remove
two moles of HX from a dihalide substrate.

Two different starting materials can be useda vicinal

dihalide or a geminal dihalide.

E2 Reactions and Alkyne Synthesis

Stronger bases are needed to synthesize alkynes by

dehydrohalogenation than are needed to synthesize
alkenes.
The typical base used is NH2 (amide), used as the sodium
salt of NaNH2. KOC(CH3)3 can also be used with DMSO as
solvent.

E2 Reactions and Alkyne Synthesis

Example of dehydrohalogenation of dihalides to afford alkynes

Elimination Reactions
Promoting Factors
Base
Solvent
Substrate
Leaving group

E1

E2

Weak base works

Strong base requires

Good ionising

Wide variety

3>2

3>2>1

Good one required

Characteristics
Kinetics

1st order

Orientation

Most highly substituted alkene

Stereochemistry
Rearrangement

2nd order

No special geometry
common

impossible